Polypropylene or polyester compositions of improved dyeability containing a linear polyamide and a linear sulfonated polyamide



United States Patent Ofiice 3,328,484 Patented June 27, 1967POLYPROPYLENE O R fiOLYESTER COMPOSI- TIONS F IMPROVED DYEABILITY CON-TAINING A LINEAR POLYAMIDE AND A LINEAR SULFONATED POLYAMIDE MauriceAlliot-Lugaz and Pierre Allard, Lyon, France,

assiglor to Societe Rhodiaceta, Paris, France, a French body corporateNo Drawing. Filed Feb. 10, 1964, Ser. No. 343,465

Claims priority, application France, Jan. 3, 1963,

20,376 19 Claims. (Cl. 260857) This application is acontinuation-in-part of our application Ser. No. 332,894, filed Dec. 23,1963, now abancloned.

This invention relates to spinnable and film-forming compositions ofimproved dyeability containing a major proportion of polypropylene or asynthetic linear polyester and the shaped articles obtained therefrom.

Synthetic linear polyesters derived from aromatic dicarboxylic acids canbe used to produce oriented structures, such as yarns, fibres and films,which are difficult to dye by conventional methods, because the dyeingafiinity of the polyester is low or nonexistent.

One of the simplest of the many processes developed for improving theafiinity of polyesters for dyes consists in incorporating in thepolyesters, before extrusion from 3% to 7% of a polyox-amide containinga tertiary nitrogen atom in its chain. These compositions give fibreswhich, as compared with unmodified polyester fibres, have an improvedafiinity for acid dyes. However, dark shades cannot be obtained usingsuch modified polyesters, and the colours are in fact scarcely deeperthan those obtained on yarns obtained from unmodified polyesters. I

Crystalline olypropylenes, prepared by polymerisation of propylene inthe presence of steresospecific catalysts, may be converted intooriented structures such as yarns, fibres and films which possessexcellent mechanical properties. However, the development of thesevarious applications has not up to the present been so far-reaching asmight have been expected. This is because of the difiiculty of dyeingthese structures, which has not yet been satisfactorily resolved.

A number of solutions have already been proposed. For example, it hasbeen suggested to use either special dyes or special dyeing methods.Attempts have also been made to increase the afiinity of polypropylenefor dyes by incorporating an adjuvant which may be, for example, adicarbox-ylic acid, a halogenated aliphatic compound, or a modifyingpolymer. If a modifying polymer is employed, difficulties incompatibility are frequently encountered. For example, when attempts aremade to prepare compositions based on polypropylene andpolyhexamethylene adipamide, it is found that it is necessary to usemixing techniques using high pressures, which are complex and expensive.

The present invention provides compositions of improved dyeability withdisperse, basic, acidic, and metallized dyestuffs which comprise (A) amajor proportion by weight of crystalline polypropylene or a syntheticlinear polyester derived from an aromatic dicarboxylic .acid and analiphatic or cycloaliphatic diol, and (B) a minor proportion by Weightof a mixture of (i) a synthetic linear polyamide or copolyamide and (ii)not more than an equal weight of a synthetic linear copolyamide of whichto 35% by weight consists of units of the formula:

in which A and B, which may be the same or different, are each CO- orNH, and M is an alkali metal. The polypropylene or synthetic linearpolyester is hereinafter referred to as the major connstituent. Theproportion of the major constituent in the compositions is preferablyfrom 70% to by weight.

The polyesters are obtained from aromatic dicarboxylic acids or theirdiesters, especially those of the formula:

R O-CO(CH ),,-Ar(CH -COOR in which R, and R represent hydrogen atoms oralkyl groups containing from 1 to 10 carbon atoms, n and m eachrepresent an integer from 0 to 4, and Ar represents a divalent aromaticradical, and glycols, preferably polymethylene glycols containing from 2to 8 carbon atoms or cisor trans-cycloaliphatic diols.

The melt viscosity of the polypropylene, measured in accordance with thestandard ASTM D-1328-52 T, may vary between wide limits but, in orderthat the preparation and conversion of these compositions may notnecessitate excessive temperatuers or pressures, use is ordinarily madeof polypropylene whose melt viscosity is between 0.1 and 8 andespecially from 0.5 to 2.

The mixture of polyamides consists, at least to the extent of one half,of a synthetic, linear poly-amide or copolyamide, derived from at leastone amino-carboxylic acid, or at least one salt of a dicarboxylic acidand a diamine, or both. As preferred examples of such polyamides, theremay be mentioned polycaprolactam, polyhexamethylene adipamide, acopolyamide from hexamethylene diamine adipate and sebacate, and acopolyamide from hexamethylene diamine adipate and captolactam.

The sulphonated synthetic, linear copol-yamide (ii), which preferablymakes up 10 to 50% by weight of the mixture (B), preferably contains inits chain units of the formula:

solos SOsK the remaining units in the copolyamide chain being derivedfrom hexamethylene diamine, and either adipic or isophthalic acid.

The ternary compositions of the invention have many advantages overknown binary compositions prepared from polyamides and polyesters orpolypropylene. If, in the known binary compositions, the polyamidesemployed are ordinary polyamides, the compositions obtained give yarnswhich have only a small superiority in dyeing afiinity to unmodifiedpolyester yarns. With polypropylene, a considerable increase indyeability is observed with acid dyes but difiiculties in preparing thecompositions .are encountered. On the other hand, if the polyamides aresulphonated polyamides, the compositions obtained are difficult toextrude, because the compatibility of the polymers is not very good, andthe yarns, obtained therefrom using the special techniques necessaryhave affinity only for basic dyes.

In contrast, the ternary compositions of the present invention are veryhomogeneous and .are similar to true alloys. Yarns, films and fibresobtained therefrom have, moreover, an afiinity not only for basic dyesbut also for acidic, metallized and disperse dyes. The mechanicalproperties of the yarns and fibres obtained from the ternarycompositions of the invention ,are not appreciably different from thoseof yarns and fibres made of the major constituent only. The tendency topill, observed on fabrics obtained from pure or blended polyesterfibres, is much less marked on fabrics obtained from fibres pres paredby extrusion of the compositions of the present invention. More over,the thermal aging resistance of polypropylene-containing filaments ofthe invention is appreciably higher than that of filaments of purepolyproylene or of. the known binary polypropylene compositions.

The following examples illustrate the invention. The percentages are byweight.

EXAMPLE 1 There are prepared by malaxation at 270 C. in a malaxator ofthe Komalaxeur Buss type compositions comprising, by weight:

(A) 80% of ethylene polyterephthalate and 20% of a copolyamide obtainedby polycondensation of 45% of hexamethylene diamine adipate and 55% ofhexamethylene diamine sebacate;

(B) 95% of ethylene polyterephthalate and of a sulphonated copolyamideobtained by polycondensation of 60% of hexamethylene diamine adipate and40% of hexamethylene diamine m-(potassium sulpho)-isophthalate; and

(C) 80% of ethylene polyterephthalate, 5% of the sulphonated copolyamidedefined for (B) and 15% of copolyamide similar to that defined for (A).

After granulation, these com-positions are extruded at 295 C. through a7-hole nozzle. The filaments obtained are stretched at 100 m./min. 3.8times.

Yarns of ethylene polyterephthalate, referred to as (D), are alsoprepared under similar conditions.

Specimens of these various yarns are dyed at 100 C. in a bath containing2% of the basic dye marketed under the trade name Bleu Basacryl GL,Basic blue'54 (Colour Index S. 175-1963). Yarns A and D are dyed dullwhite. Yarn B is dyed blue, and yarn C is dyed an intense blue.

EXAMPLE 2 There are prepared by malaxation the following compositionscomprising, by weight:

(A) 80% of ethylene polyterephthalate, 5% of a sulphonated copolyamideobtained by polycondensation of 60% of hexamethylene diamine adipate and40% of hexamethylene diamine m-(potassium sulpho)-isophthalate, and 15%of a copolyamide obtained by polycondensation of 80% of hexamethylenediamine adipate and 20% of hexamethylene diamine sebacate;

(B) 80% of ethylene polyterephthalate, 5 of a sulphonated'polyarnide'identical to that defined under (A), and 15% of acopolyamide obtained by polycondensation of 80% of hexamethylene diamineadipate and 20% of caprolactam.

These compositions are extruded at 280 C. to form yarns, which 'are thenstretched 4 times. Under substan-- tially identical conditions, a yarnof ethylene polyterephthalate, referred to as (C) is prepared.

Specimens of each of these yarns are dyed at 130 C. in a bath comprising2% of the basic dye marketed under the trade name Bleu Basacryl GL. Adark blue-violet coloration is obtained on the yarns (A) and (B), butyarn (C) is only dyed slightly pink.

EXAMPLE 3 There are prepared by malaxation the following compositionscomprising, by Weight:

(A) 80% of ethylene polyterephthalate, 5% of a sulphonat'ed copolyamideobtained by polycondensation of 90% of hexamethylene diamineisophthalate and of hexamethylene diamine 'm-(potassium sulpho)isophthalate, and of a copolyamide obtained by poly-' condensation of 45of hexamethylene diamine adipate and 55% of hexamethylene diaminesebacate;

(B) 80% of ethylene poly-terephthalate and of the unsulphonatedcopolyamide defined under (A).

These compositions are extruded between 265 and 285 C. through a 7-holenozzle and the yarns obtained are stretched. Yarns of ethylenepolyterephthalate, referred to as (C), are prepared under similarconditions. The dynamometric properties of the yarns obtained are asfollows:

Yarn Extent of Strength in Elongation,

stretch g. [denier percent Yarn Acid dye Metulliferous dye Basie dye CWhite Pale mauve Pink. A Light hlue Dark violet-blue. Dark violet-blue.B Pale blue do Pink.

EXAMPLE 4 The following compositions are prepared as in the precedingexamples:

(A) 74% of polyethylene tereph-thalate, 15% of a copolyamide preparedfrom 45% of hexamethylene diamine adipate and 55% of hexamethylenediamine sebactate, and 11% of a sulphonated copolyamide prepared bypolycondensation of of hexamethylene diamine isophthalate and 10% ofhexamethylene diamine m-(po' tassium sulpho)-isophthalate;

(B) 74% of ethylene polyterephthalate, 15% of a copolyamide preparedfrom 80% by weight of hexamethylene diamine adipate and 20% by weight ofcaprolactam, and 11% by weight of the sulphonated copolyamide definedunder (A).

Yarns are prepared by microspinning these compositions, and alsostandard polyethylene terepht-halate. Specimens of these yarns are dyedat C. in a bath comprising 1% of the disperse dye marketed under thetrade name Bleu Latyl FL (Disperse Blue 27, Colour Index S. 210-1963).An intense blue coloration is observed on yarns A and B, while thestandard remains substantially undyed.

EXAMPLE 5 by polycondensation of 60% by weight of hexamethylene Idiamine adipate and 40% by weight of hexamethylene diamineIii-(potassium snlpho)-isophthalate.

The constituents are mixed as grains, ground in an apparatus of theLancellin type, and then malaxa-ted in a micro-malaxator at temperaturesbetween and 275 C. The compositions obtained are extruded at 310 C.

through a spinneret having 7 holes, each 0.3 mm. in diameter. Aftercooling, the filaments are stretched four times on a finger heated to 90C.

The filaments are dyed in baths containing 5% of o-phenylphenol, andeither (I) 3% of Bleu Latyl FL, a disperse dye marketed by E. I. du Pontde Nemours and Company, Disperse Blue 27 (Cl. S. 210 -1963); or

(II) 3% of Rouge Basacryl GL, a basic dye marketed by B.A.S.F. Basic Red29 (Cl. S. 163l963); or

(III) 3% of Rouge Vialon Solide B, a metalliferous dye marketed byB.A.S.F. (C.I. No. 225, 2nd edition, 1956); or

(IV) 3 of Bleu Pur Lanasyne GL, an acid dye marketed by Sandoz (C.I. No.127, 2nd edition, 1956),

and the colours of the filaments obtained are given in the followingtable.

We claim:

1. Compositions of improved dyeability which comprise (A) a majorproportion by weight of a polymer selected from the class consisting ofcrystalline polypropylene and a synthetic linear polyester derived froman aromatic dicarboxylic acid and a diol selected from the classconsisting of aliphatic and cycloaliphatic diols, and (B) a minorproportion by weight of a mixture of (i) a synthetic, linear polyamide,and (ii) not more than an equal Proportions of the constituents in thecompositions from which the filaments Dye I Dye II Dye III Dye IV aremade 100% A Undyed Very light pink Undyed. Undyed. 90% A/% B(i) BlueLight pink Dark red Light blue. 87% A 10% B(i)/3% B(ii) Dark blue- Darkred do Dark blue. 87% A/7% B(i) 6% B(ii) Bright red do Medium blue.

EXAMPLE 6 weight of a synthetic, linear copolyamide of which 5% to byweight consists of units of the formula:

Under conditions identical with those of Example 5, filaments areprepared from compositions containing the following polymers:

(A) polypropylene having a melt viscosity of 1.2;

(B)(i) a copolyamide obtained by polycondensation of 22% by weight ofhexamethylene diamine adipate and 78% by Weight of caprolaotam; and (ii)a sulphonated copolyamide identical with that used in Example 1.

These filaments are dyed as in Example 5 with dyes II and IV, and thecolours of the filaments obtained are shown in the following table.

The fastness of the shades obtained to friction and light is very good.

EXAMPLE 7 A com-position is prepared from: 87 parts by weight ofpolypropylene having a melt viscosity of 0.8, 10 parts by weight of acopolyamide obtained by polycondensation of 22% by weight ofhexamethylene diamine adipate and 78% by weight of caprolaotam and 3parts by weight of the sulphonated copolyamide described in Example 5,by crushing and malaxation in an apparatus of the Komalaxeur Buss type,at 165237 C.

This composition is extruded at 400 m./min. through a spinneretemaintained at 300 C., and the filaments obtained are stretched 4.6 timesat 240 m./min. A specimen of these filaments is dyed in a bathcomprising 5% by weight of orthophenylphenol and 3% by weight of RougeAstrazon DBL, marketed by the company Bayer (C.I. Basic Violet 7, 2ndedition, 1956), and they are coloured a bright red colour, Whereasfilaments of pure polypropylene are scarcely dyed at all.

The filaments obtained in this example have a breaking strangth of 6.35g./denier at an elongation of 16.2%. Filaments of pure polypropyleneprepared under similar conditions have a strength of 6.22 g./denier andan elongation of 26%. In addition, when filaments of pure polypropyleneare subjected to thermal aging in an Oven at 110 C., they are degradedat the end of 4 days, while filaments made from the ternary compositionof Example 7 are degraded only after 33 days.

l S OaM in which A and B are each selected from the class consisting ofCO and -NH-, and M is an alkali metal.

2. Polyester compositions which comprise (A) a major proportion byweight of a synthetic linear polyester derived from ana-romaticdicarboxylic acid and a diol selected from the class consisting ofaliphatic and cycloaliphatic diols, and (B) a minor proportion by weightof a mixture of (i) a synthetic, linear polyamide, and (ii) not morethan an equal weight of a synthetic, linear copolyamide of which 5% to35 by weight consists of units of the formula:

in which A and B are each selected from the class consisting of CO and-NH, and M is an alkali metal.

3. Polypropylene compositions which comprise (A) a major proportion byweight of crystalline polypropylene, and (B) a minor proportion byweight of a mixture of (i) a synthetic, linear polyamide, and (ii) notmore than an equal weight of a synthetic, linear copolyamide of which 5%to 35% by weight consists of units of the formula:

| S OaM in which A and B are each selected from the class consisting ofCO- and --NH-, and M is an alkali metal.

4. Polyester compositions as claimed in claim 2 comprising 70 to byweight of the synthetic linear polyester.

5. Polypropylene compositions as claimed in claim 3 comprising -70 -to95% by weight of crystalline polypropylene.

6. Polyester compositions as claimed in claim 2 in which the syntheticlinear polyester is polyethylene terephthalate.

7. Polypropylene compositions as claimed in claim 3 in which the meltviscosity of the polypropylene is 0.5

-8. Polyester compositions as claimed in claim 2 in which the mixture(B) comprises to 50% by weight of the copolyamide (ii).

9. Polypropylene compositions as claimed in claim 3 in which the mixture(B) comprises 10 to 50% by weight of the copolyamide (ii).

10. Polyester compositions as claimed in claim 2,in which the syntheticlinear polyamide (i) is selected from the class consisting ofpolycapr-olactarn, polyhexamethylene adipamide, a copolyamide fromhexamethylene diamine adipate and sebacate, and a copolyamide fromhexamethylene diamine adipate and caprolactam.

11. Polypropylene compositions as claimed in claim 3 in which thesynthetic linear polyamide (i) is selected from the class consisting ofpolycaprolactam, polyhexamethylene adipamide, a copolyamide fromhexamethylene ,diamine adipate and sebacate, and a copolyamide fromhexamethylene diamine adipate and caprolactam.

12. Polyester compositions as claimed in claim 2 in which the syntheticlinear copolyamide (ii) is derived from an isophthalate selected fromthe class consisting of hexamethylene diamine m-(sodium and potassiumsulpho)-isophthalates and a hexamethylene diamine salt selected from theclass consisting of hexamethylene diamine adipate andhexamethylenediamine isophthalate.

13. Polypropylene compositions as claimed .in claim 3 in which thesynthetic linear copolyamide (ii) is derived from an isophthalateselected from the class consisting of hexamethylene diamine m-(sodiumand potassium sulpho)- isophthalates and from hexamethylene diamineadipate.

14. Polyester compositions which comprise (A) 70 to 95% by weight ofpolyethylene terephthalate, and (B) '5 to 30% by Weight of a mixture of(i) 55 to 90% by weight of a synthetic linear polyarnide selected fromthe class consisting of polycaprolactam, polyhexamethylene adipamide, acopolyamide from hexamethylene diamine adipate and sebacate and acopolyamine from hexamethylene diamine adipate and caprolactam, and (ii)10 to 45% by Weight of a synthetic linear copolyamide selected from theclass consisting of copolyamides derived from an isophthalate selectedfrom the class consisting of hexamethylene diamine m-(sodium andpotassium sulpho)-isophthalates and a hexamethylene diamine saltselected fromthe class consisting of hexamethylene diamine adipate andhexamethylene diamine isophthalate, 5 to 35% bylweight of the saidcopolyamide consisting of units of the formula:

in which M is an alkali metal selected 'from the class consisting ofsodium and potassium.

15. Polyester compositions and shaped articles made therefrom dyed witha dyestuif selected from the class consisting of disperse, basic,acidic, and metallized dyestufis, said polyester compositi-oncomprising(A) a major proportion by Weight of a synthetic linear polyester derivedfrom an aromatic dicarboxylic acid and a diol selected from the classconsisting of aliphatic and cycloaliphatic diols, and (B) a minorproportion by Weight of a mixture of (i) a synthetic, linear polyamide,and (ii) not more than an equal weight of a synthetic, linearcopolyamide of E which 5% to 35% by weight consists of units of theformula:

in which A and B are each selected from the class consisting of -CO andNH, and M is an alkali metal.

16. Polyester compositions and shaped articles made there-from dyed witha dyestuff selected from the class consisting of disperse, basic,acidic, and metallized dyestutfs, said polyester composition comprising(A) to 95 by weight of a polyethylene terephthalate, and (B) 5 to 30% byWeight of a mixture of (i) 55 to by weight of a synthetic linearpolyamide selected from the class consisting of polycaprolactam,polyhexamethylene adipamide, a copolyamide from hexamethylene diamineadipate and sebacate and a copolyamide from hexamethylene diamineadipate and caprolactam, and (ii) 10 to 45% by weight of va syntheticlinear copolyamide selected from the class consisting of copolyamidesderived from an isophthalate selected from the class consisting ofhexamethylene diamine m-(sodium and potassium sulpho)-isophthalates anda hexamethylene diamine salt selected from the class consisting ofhexamethylene diamine adipate and hexamethylene diamine isophthalate, 5to 35% by weight of the said copolyamide consisting of units of theformula:

l SO M in which M is an alkali metal selected from the class con 7sisting of sodium and potassium.

17. Polypropylene compositions which comprise (A) 70 to by Weight ofcrystalline polypropylene of melt viscosity 0.5 to 2, and (B) 5 to 30%by weight of a mixture of (i) 50 to 90% by weight of a synthetic linearpolyamide in which M is an alkali metal selected from the classconsisting of sodium and potassium.

18. Polypropylene compositions and shaped articles made therefrom dyedwith a dyestuff selected from the class consisting of disperse, basic,acidic, and metallized dyestuffs, said polypropylene compositionscomprising (A) a major proportion by weight of crystalline propylene,

and (B) a minor proportion by Weight of a mixture of (i) a synthetic,linear polyamide, and (ii) not more thanan equal weight of a synthetic,linear copolyamide of 9 which to 35% by weight consists of units of theformula in which A and B are each selected from the class consisting of-CO- and NH, and M is an alkali metal.

19. Polypropylene compositions and shaped articles made therefrom with adyestufi selected from the class consisting of disperse, basic, acidic,and metallized dyestuffs, said polypropylene compositions comprising (A)70 to 95% by weight of crystalline polypropylene of melt viscosity 0.5to 2, and (B) 5 to 30% by weight of a mixture of (i) 50 to 90% by Weightof a synthetic linear polyamide selected from the class consisting ofpolycaprolactam, polyhexamethylene adipamide, a copolyamide fromhexamethylene diamine adipate and sebacate, and a copolyamide fromhexamethylene diamine adipate and caprolactam, and (ii) to 40% by weightof a synthetic linear copolyamide selected from the class consisting ofcopolyami'des derived from an isophthalate selected from the classconsisting of hexamethylene diamine m- (sodium and potassiumsulpho)-isophthalates and from hexamethylene diamine adipate, 5 to byweight of the said copolyamide consisting of units of the formula:

S OaM in which M is an alkali metal selected from the class consistingof sodium and potassium.

References Cited UNITED STATES PATENTS MURRAY TILLMAN, Primary Examiner.

P. LIEBERMAN, Assistant Examiner.

1. COMPOSITIONS OF IMPROVED DYEABILITY WHICH COMPRISE (A) A MAJORPROPORTION BY WEIGHT OF A POLYMER SELECTED FROM THE CLASS CONSISTING OFCRYSTALLINE POLYPROPYLENE AND A SYNTHETIC LINEAR POLYSTER DERIVED FROMAN AROMATIC DIACARBOXYLIC ACID AND A DIOL SELECTED FROM THE CLASSCONSISTING OF ALIPHATIC AND CYCLOALIPHATIC DIOLS, AND (B) A MINORPROPORTION BY WEIGHT OF A MIXTURE OF (I) A SYNTHETIC, LINEAR POLYAMIDE,AND (II) NOT MORE THAN AN EQUAL WEIGHT OF A SYNTHETIC, LINEARCOPOLYAMIDE OF WHICH 5% TO 35% BY WEIGHT CONSISTS OF UNITS OF THEFORMULA: